Skip to main content

Advertisement

Log in

Characterization of Limonoids in Citrus Essential Oils by Means of Supercritical Fluid Chromatography Tandem Mass Spectrometry

  • Published:
Food Analytical Methods Aims and scope Submit manuscript

Abstract

The dual purpose of this research was to investigate the presence of limonoid aglycones in Citrus essential oils and to develop a rapid and reliable SFC-APCI-QqQ MS method for their characterization. In this study, 12 limonoid aglycones were tentatively identified in 11 different citrus essential oils. The developed method allowed a very fast separation in less then 7 min with a very low amount of organic solvent. Calibration curve of limonin was constructed by using a triple quad MS detector in order to quantify the limonin content in the analyzed samples. The content of limonin ranged from 0.5 (clementine essential oil) to 21.2 mg L−1 (bergamot essential oil) in the cold-pressed Citrus essential oils analyzed. Moreover, product ion scan (PIS) acquisition mode was also used for the structure elucidation of isobaric compounds. To the best of our knowledge, this is the first investigation on limonoid aglycones in Citrus essential oils.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  • Adorjan B, Buchbauer G (2010) Biological properties of essential oils: an updated review. Flavour Fragr J 25:407–426

    Article  CAS  Google Scholar 

  • Balestrieri E, Pizzimenti F, Ferlazzo A, Giofrè SV, Iannazzo D, Piperno A, Romeo R, Chiacchio MA, Mastino A, Macchi B (2011) Antiviral activity of seed extract from Citrus bergamia towards human retroviruses. Bioorg Med Chem 19:2084–2089

    Article  CAS  PubMed  Google Scholar 

  • Battinelli L, Mengoni F, Lichtner M, Mazzanti G, Saija A, Mastroianni CM, Vullo V (2003) Effect of limonin and nomilin on HIV-1 replication on infected human mononuclear cells. Planta Med 69:910–913

    Article  CAS  PubMed  Google Scholar 

  • Bilal H, Akram W, Hassan SA, Sahar S, Iqbal MM (2013) Determination of Limonoids and Nomilin contents in different Citrus cultivars using high performance liquid chromatography. Pak J Sci Ind Res 56:36–40

    CAS  Google Scholar 

  • Breksa AP III, Hidalgo MB, Lee YM (2009) Liquid chromatography-electrospray ionization mass spectrometry method for the rapid identification of citrus limonoid glucosides in citrus juices and extracts. Food Chem 117:739–744

    Article  CAS  Google Scholar 

  • Breksa AP III, Kahn T, Zukas AA, Hidalgo MB, Yuen ML (2011) Limonoid content of sour orange varieties. J Sci Food Agric 91:1789–1794

    Article  CAS  PubMed  Google Scholar 

  • Donato P, Dugo P, Cacciola F, Dugo G, Mondello L (2009) High peak capacity separation of peptides through the serial connection of LC columns under high temperature. J Sep Sci 32:1129–1136

    Article  CAS  PubMed  Google Scholar 

  • Dreyer DL (1996) Citrus bitter principles–V. Botanical distribution and chemotaxonomy in the Rutaceae. Phytochemistry 5:367–378

    Article  Google Scholar 

  • Dugo G, Di Giacomo A (2002) Citrus: the genus Citrus. Taylor & Francis, London

    Google Scholar 

  • Dugo G, Mondello L (2010) Citrus oils: composition, advanced analytical techniques, contaminants, and biological activity. Taylor & Francis, Boca Raton

    Book  Google Scholar 

  • Dugrand A, Orly A, Duval T, Hehn A, Froelicher Y, Bourgaud F (2013) Coumarin and furocoumarin quantitation in citrus peel via ultraperformance liquid chromatography coupled with mass spectrometry (UPLC-MS). J Agric Food Chem 61:10667–10684

    Article  CAS  Google Scholar 

  • Frérot E, Decorzant E (2004) Quantification of total furocoumarins in Citrus oils by HPLC coupled with UV, fluorescence, and mass detection. J Agric Food Chem 52:6879–6889

    Article  CAS  PubMed  Google Scholar 

  • Giuffrida D, Zoccali M, Giofrè SV, Dugo P, Mondello L (2017) Apocarotenoids determination in Capsicum chinense Jacq. cv. Habanero, by supercritical fluid chromatography-triple-quadrupole/mass spectrometry. Food Chem 231:316–323

    Article  CAS  PubMed  Google Scholar 

  • Govindachari TR, Suresh G, Banumathi B, Masilamani S, Gopalakrishnam G, Kumari GNK (1999) Antifungal activity of some B,D-Seco Limonoids from two Meliaceous plants. J Chem Ecol 25:923–933

    Article  CAS  Google Scholar 

  • Hasegawa S, Bennett RD, Verdon CP (1980) Limonoids in Citrus seeds: origin and relative concentration. J Agric Food Chem 28:922–925

    Article  CAS  Google Scholar 

  • Kikuchi T, Ueno Y, Hamada Y, Furukawa C, Fujimoto T, Yamada T, Tanaka R (2017) Five new Limonoids from peels of Satsuma Orange (Citrus reticulata). Molecules 22:907–916

    Article  CAS  Google Scholar 

  • Kim J, Jayaprakasha GK, Patil BS (2013) Limonoids and their anti-proliferative and antiaromatase properties in human breast cancer cells. Food Funct 4:258–265

    Article  CAS  PubMed  Google Scholar 

  • Lam LKT, Li Y, Hasegawa S (1989) Effects of Citrus Limonoids on glutathione S-transferase activity in mice. J Agric Food Chem 37:878–880

    Article  CAS  Google Scholar 

  • Lesellier E, West C (2015) The many faces of packed column supercritical fluid chromatography - a critical review. J Chromatogr A 1382:2–46

    Article  CAS  PubMed  Google Scholar 

  • Manners GD, Breska AP III (2004) Identifying Citrus Limonoid Aglycones by HPLC-EI/MS and HPLC-APCI/MS techniques. Phytochem Anal 15:372–381

    Article  CAS  PubMed  Google Scholar 

  • Manners GD, Breska AP III, Schoch TK, Hidalgo MB (2003) Analysis of bitter Limonoids in Citrus juices by atmospheric pressure chemical ionization and electrospray ionization liquid chromatography-mass spectrometry. J Agric Food Chem 51:3709–3714

    Article  CAS  PubMed  Google Scholar 

  • Miller EG, Porter JL, Binnie WH, Guo IY, Hasegawa S (2004) Further studies on the anticancer activity of Citrus Limonoids. J Agric Food Chem 52:4908–4912

    Article  CAS  PubMed  Google Scholar 

  • Moodley VE, Mulholland DA, Raynor MW (1995) Micellar electrokinetic capillary chromatography of limonoid glucosides from citrus seeds. J Chromatogr A 718:187–193

    Article  CAS  Google Scholar 

  • Mustafa NEM (2015) Citrus essential oils: current and prospective uses in the food industry. Recent Pat Food Nutr Agric 7:115–127

    Article  CAS  PubMed  Google Scholar 

  • Raynor MW, Roberts SL, Mulholland DA (1993) Capillary supercritical fluid chromatography of limonoids. J High Resolut Chromatogr 16:469–472

    Article  CAS  Google Scholar 

  • Ren W, Xin S, Han L, Zuo R, Li Y, Gong M, Wei X, Zhou Y, He J, Wang H, Si N, Zhao H, Yang J, Bian B (2015) Comparative metabolism of four limonoids in human liver microsomes using ultra-high-performance liquid chromatography coupled with high-resolution LTQ-Orbitrap mass spectrometry. Rapid Commun Mass Spectrom 29:2045–2056

    Article  CAS  PubMed  Google Scholar 

  • Rouseff RL (1982) Nomilin, a new bitter component in grapefruit juice. J Agric Food Chem 30:504–507

    Article  CAS  Google Scholar 

  • Rouseff RL, Nagy S (1982) Distribution of limonoids in citrus seeds. Phytochemistry 21:85–90

    Article  CAS  Google Scholar 

  • Russo M, Torre G, Carnovale C, Bonaccorsi I, Mondello L, Dugo P (2012) A new HPLC method developed for the analysis of oxygen heterocyclic compounds in Citrus essential oils. J Essent Oil Res 24:119–129

    Article  CAS  Google Scholar 

  • Russo M, Bonaccorsi I, Torre G, Sarò M, Dugo P, Mondello L (2014) Underestimated sources of flavonoids, limonoids and dietary fibre: availability in lemon's by-products. J Funct Foods 9:18–26

    Article  CAS  Google Scholar 

  • Russo M, Bonaccorsi I, Costa R, Trozzi A, Dugo P, Mondello L (2015a) Reduced time HPLC analyses for fast quality control of citrus essential oils. J Essent Oil Res 27:307–315

    Article  CAS  Google Scholar 

  • Russo M, Bonaccorsi I, Inferrera V, Dugo P, Mondello L (2015b) Underestimated sources of flavonoids, limonoids and dietary fiber: availability in orange’s by-products. J Funct Foods 12:150–157

    Article  CAS  Google Scholar 

  • Russo M, Arigò A, Calabrò ML, Farnetti S, Mondello L, Dugo P (2016) Bergamot (Citrus bergamia Risso) as a source of nutraceuticals: limonoids and flavonoids. J Funct Foods 20:10–19

    Article  CAS  Google Scholar 

  • Tarafder A (2016) Metamorphosis of supercritical fluid chromatography to SFC: an overview. TrAC, Trend Anal Chem 81:3–10

    Article  CAS  Google Scholar 

  • Tranchida PQ, Zoccali M, Bonaccorsi I, Dugo P, Mondello L, Dugo G (2013) The off-line combination of high performance liquid chromatography and comprehensive two-dimensional gas chromatography–mass spectrometry: a powerful approach for highly detailed essential oil analysis. J Chromatogr A 1305:276–284

    Article  CAS  PubMed  Google Scholar 

  • Vikram A, Jayaprakasha GK, Patil BS (2007) Simultaneous determination of citrus limonoid aglycones and glucosides by high performance liquid chromatography. Anal Chim Acta 590:180–186

    Article  CAS  PubMed  Google Scholar 

  • Yu J, Wang L, Walzem RL, Miller EG, Pike LM, Patil BS (2005) Antioxidant activity of Citrus Limonoids. J Agric Food Chem 53:2009–2014

    Article  CAS  PubMed  Google Scholar 

  • Zoccali M, Bonaccorsi IL, Tranchida PQ, Dugo P, Mondello L, Dugo G (2015) Analysis of the sesquiterpene fraction of citrus essential oils by using the off-line combination of high performance liquid chromatography and gas chromatography-based methods: a comparative study. Flavour Fragr J 30:411–422

    Article  CAS  Google Scholar 

  • Zoccali M, Giuffrida D, Dugo P, Mondello L (2017) Direct online extraction and determination by supercritical fluid extraction with chromatography and mass spectrometry of targeted carotenoids from red habanero peppers (Capsicum chinense Jacq.). J Sep Sci 40:3905–3913

    Article  CAS  PubMed  Google Scholar 

Download references

Acknowledgments

We gratefully thank Shimadzu and Merck KGaA corporations for their continuous support. Adriana Arigò thanks the “Prof. Antonio Imbesi Foundation” of the University of Messina for the financial support. Fabio Salafia tanks the “Programma Operativo Fondo Sociale Europeo (FSE) Regione Sicilia 2014-2020-Asse 3 Ob. 10.5” for thefinancial support.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Luigi Mondello.

Ethics declarations

Conflict of Interest

Mariosimone Zoccali declares that he has no conflict of interest. Adriana Arigò declares that she has no conflict of interest. Marina Russo declares that she has no conflict of interest. Fabio Salafia declares that he has no conflict of interest. Paola Dugo declares that she has no conflict of interest. Luigi Mondello declares that he has no conflict of interest.

Ethical Approval

This article does not contain any studies with human or animal subjects.

Informed Consent

Not applicable.

Electronic supplementary material

ESM 1

(PPTX 69 kb)

ESM 2

(PPTX 157 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zoccali, M., Arigò, A., Russo, M. et al. Characterization of Limonoids in Citrus Essential Oils by Means of Supercritical Fluid Chromatography Tandem Mass Spectrometry. Food Anal. Methods 11, 3257–3266 (2018). https://doi.org/10.1007/s12161-018-1303-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12161-018-1303-1

Keywords

Navigation